CN103088445A - Preparation method for metallocene linear low density polyethylene sub-micron fibers - Google Patents
Preparation method for metallocene linear low density polyethylene sub-micron fibers Download PDFInfo
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- CN103088445A CN103088445A CN201310067619XA CN201310067619A CN103088445A CN 103088445 A CN103088445 A CN 103088445A CN 201310067619X A CN201310067619X A CN 201310067619XA CN 201310067619 A CN201310067619 A CN 201310067619A CN 103088445 A CN103088445 A CN 103088445A
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- 239000000835 fiber Substances 0.000 title claims abstract description 47
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 21
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000155 melt Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 238000001523 electrospinning Methods 0.000 abstract description 5
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- -1 polyethylene Polymers 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000006196 drop Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
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Abstract
本发明公开了一种茂金属基低密度聚乙烯亚微米纤维的制备方法：利用熔体静电纺丝装置，加热料筒到一定温度，加入一定量的mLLDPE原料，加热30min，使mLLDPE在料筒内熔融，再加入聚乙烯蜡作为润滑剂，当熔体开始通过喷头向下滴出时，打开高压电源，加上一定电压，使熔体在高压静电的作用下喷射到接收装置上，得到mLLDPE亚微米纤维；利用该方法得到的亚微米纤维形貌良好，粗细均匀，表面较为光滑，且制备方法简单，原料易得，成本低廉，有利于静电纺丝工业化，具有广阔的应用前景。
The invention discloses a method for preparing metallocene-based low-density polyethylene submicron fibers: using a melt electrospinning device, heating the barrel to a certain temperature, adding a certain amount of mLLDPE raw material, and heating for 30 minutes to make the mLLDPE in the barrel Melt inside, then add polyethylene wax as a lubricant, when the melt starts to drip down through the nozzle, turn on the high-voltage power supply, apply a certain voltage, so that the melt is sprayed onto the receiving device under the action of high-voltage static electricity, and mLLDPE is obtained Submicron fiber: The submicron fiber obtained by this method has good shape, uniform thickness, relatively smooth surface, simple preparation method, easy-to-obtain raw materials, and low cost, which is conducive to the industrialization of electrospinning and has broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers.
Background technology
The linear low density polyethylene of utilizing metallocene catalyst polymerisation to obtain, side chain is evenly distributed, molecular weight distribution is narrower, and have good toughness, an anti-ESC ability, higher impact strength, tearing strength, TENSILE STRENGTH, good rigidity, creep resisting ability and good processing characteristics, the development of mLLDPE in recent years is very fast, is little by little replacing the conventional polyethylene kind.
Electrostatic spinning technique claimed again electrospinning, is a kind of important method for preparing superfine fibre and nanofiber, from the proposition of its basic thought more than 70 year till now.The nineties in 20th century, along with the attention of people to nanosecond science and technology, some researchers begin to notice that electrostatic spinning is in the great potential of nanofiber manufacture view.The basic principle of electrostatic spinning is: polymer solution or melt are subject to the high-pressure electrostatic effect, form jet from capillary end and fly to receiving system, and jet is high elongation in electric field, and solvent evaporates or melt solidify, and form superfine fibre on receiving system.Electrostatic spinning can be divided into solution electrostatic spinning and melt electrostatic spinning.The solution electrostatic spinning is widely used, and is more universal.And relatively less to the research of melt electrostatic spinning, its main cause is that comparison in equipment is complicated, is difficult to preparing nano level fiber.The method of Larrondo in 1981 and the experiment of Manley first passage has been studied the electrostatic spinning process of polymer melt, confirmed the feasibility of polymer melt electrostatic spinning, and the pattern of the forming process of the distortion of melt drop, fiber, fiber and performance etc. have been done comparatively detailed analysis.Do not use solvent in the melt electrostatic spinning process, got rid of the impact of solvent on experiment, need not to remove residual solvent from collecting fiber yet.This just means that melt electrostatic spinning is more friendly, more general to environment than solution electrostatic spinning.Develop in recent years and improve the melt electrostatic spinning technology and become study hotspot.
Summary of the invention
For the problems referred to above, the purpose of this invention is to provide a kind of novel method for preparing Metallocenyl linear low density polyethylene sub-micron fibers.
The present invention combines traditional solution electrospinning process, and with Metallocenyl linear low density polyethylene raw material high-temperature fusion, the effect of recycling electrostatic force is spun into sub-micron fibers with it.MLLDPE can't be dissolved in organic solvent at normal temperatures, can't utilize the solution method of electrostatic spinning to prepare fiber, and the melting electrostatic spinning does not need solvent can successfully obtain the sub-micron fibers of mLLDPE.
For achieving the above object, the present invention takes following technical scheme:
A kind of preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers is characterized in that utilizing the melt electrostatic spinning technology to prepare fiber, and preparation as follows:
(1) utilize melt electrostatic spinning device, controlled condition is that heating-up temperature is 0-400 ℃, and voltage is 0-50kV, and receiving range is 0-10cm;
(2) utilize melt electrostatic spinning device, first barrel is heated to design temperature, after temperature stabilization, add a certain amount of mLLDPE raw material, heating 30min makes mLLDPE melting in barrel, then adds Tissuemat E as lubricant;
(3) heating certain hour, when melt begins to ooze downwards by shower nozzle, open the high-voltage D.C. generator power supply, add certain voltage, melt is being ejected on the receiving system of certain acceptance distance under the effect of high-pressure electrostatic, obtains the mLLDPE sub-micron fibers.
Wherein, preferably, described in step (1), temperature is 150 ℃;
Preferably, described in step (1), voltage is 0-30kV;
Preferably, described in step (1), voltage is 29kV;
Preferably, described in step (1), receiving range is 3cm.
Preferably, described in step (2), the ratio of the quality of the quality of Tissuemat E and mLLDPE is 1:3.
Preferably, be 10min heat time heating time described in step (3), and voltage is 29 kV, and certain acceptance distance is 3cm.
The present invention is owing to taking above technical scheme, and it has the following advantages:
1, mLLDPE can't be dissolved in any organic solvent at normal temperatures, can't utilize solution electrospinning method to prepare fiber, and utilize the melt electrostatic spinning technology can successfully prepare sub-micron fibers;
2, the melt electrostatic spinning technology has been avoided the solvent recovery problem, with the raw material direct fabrics, need not add the composition that other may be poisonous, can guarantee the security of the fiber that spins;
3, due to the solvent-free evaporation of spinning process, fiber surface is smooth, and spinning efficiency improves greatly, has also saved the energy and cost;
4, the standby mLLDPE sub-micron fibers of melt electrostatic spinning legal system is continuous fiber, and fibre diameter is little, and specific area is large, and application prospect is wide.
Description of drawings
Fig. 1 is the SEM image of example 1;
Fig. 2 is the SEM image of example 2;
Fig. 3 is the SEM image of example 3;
Fig. 4 is melt electrostatic spinning device structural representation of the present invention.
The specific embodiment
The present invention will be further described below in conjunction with drawings and Examples.
as shown in Figure 4, the electrostatic spinning apparatus that the present invention adopts is a kind of new polymers melt electrostatic spinning device of designed, designed, mainly by incubator 1, barrel 2, nozzle 3, push rod 4, electric heating body 5, receiving system 6 and HV generator 7 form, wherein: case lid 11 and casing 12 consist of incubator 1, be fixed with barrel 2 in casing 12 by screw at the middle body of case lid 11, be bolted with nozzle 3 below barrel 2, and from the middle body of casing 12 everywhere, and by wire 31 ground connection, the top of push rod 4 is provided with handle 41 and insulated thermal insulating layer 42, the bottom body of rod 43 of push rod 4 is for becoming section shape, its top is connected with barrel 2 inner hole threads, its underpart imports nozzle 3, nozzle 3 belows of incubator 1 arrange receiving system 6, consist of by take-up reel 61 with by the height adjustable disk body 63 of screw 62, and the cathode output end of HV generator 7 connects receiving system 6, nozzle 3 ground connection, within device for spinning is placed in transparent casing 12, heat lamp is set in casing.
Spinning process is as follows: receiving system 6 connects high-voltage positive electrode, nozzle 3 ground connection; After barrel 2 is heated to default polymer melting temperature, add a certain amount of spinning material (polymeric aggregate, powder or section) in barrel 2, after heating a period of time, after polymer reaches design temperature, begin gradually melting; Rotating push-rod 4 is exerted pressure, when the polymer drop of melting appears in nozzle 3 ends, and opening high pressure electrostatic generator 7, regulation voltage ejects melt stretcher strain under the effect of electrostatic force, and cooling being deposited on receiving system 6 forms superfine fibre.
Embodiment 1
The melt spinning unit temp is set as 150 ℃, after temperature stabilization, add the mLLDPE raw material of 0.3g, heating 30min, make mLLDPE melting in barrel, add again Tissuemat E 0.1g, after heating 10min, open the high-voltage D.C. generator power supply, add certain voltage, the beginning spinning, spinning voltage 29kV, receiving range are 3cm.After the spinning certain hour, take out fiber.Fig. 1 is the SEM photo of mLLDPE fiber, and the pattern of fiber is good as can be observed from Figure, even thickness, and the surface is comparatively smooth.The average diameter of fiber is 1.01 μ m, and diameter is distributed as 0.22.
Embodiment 2
The melt spinning unit temp is set as 170 ℃, after temperature stabilization, add the mLLDPE raw material of 0.3g, heating 30min, make mLLDPE melting in barrel, add again Tissuemat E 0.1g, after heating 10min, open the high-voltage D.C. generator power supply, add certain voltage, the beginning spinning, spinning voltage 29kV, receiving range are 3cm.After the spinning certain hour, take out fiber.Fig. 2 is the SEM photo of mLLDPE fiber, and the pattern of fiber is good as can be observed from Figure, even thickness.The average diameter of fiber is 4.89 μ m, and diameter is distributed as 0.54.
Embodiment 3
The melt spinning unit temp is set as 150 ℃, after temperature stabilization, adds the mLLDPE raw material of 0.3g, heating 30min makes mLLDPE melting in barrel, then adds Tissuemat E 0.1g and nano-TiO
2Powder 0.01g after heating 10min, opens the high-voltage D.C. generator power supply, adds certain voltage, the beginning spinning, and spinning voltage 29kV, receiving range are 3cm.After the spinning certain hour, take out fiber.Fig. 3 is for adding nano-TiO
2The SEM photo of mLLDPE fiber, the pattern of fiber is good as can be observed from Figure, but does not add TiO
2The time thicker.
Above embodiment is only the representative of the specific embodiment, not as the foundation that limits claim.
Claims (7)
1. the preparation method of a Metallocenyl low density polyethylene (LDPE) sub-micron fibers, is characterized in that utilizing the melt electrostatic spinning technology to prepare fiber, and preparation as follows:
(1) utilize melt electrostatic spinning device, controlled condition is that heating-up temperature is 0-400 ℃, and voltage is 0-50kV, and receiving range is 0-10cm;
(2) utilize melt electrostatic spinning device, first barrel is heated to design temperature, after temperature stabilization, add a certain amount of mLLDPE raw material, heating 30min makes mLLDPE melting in barrel, then adds Tissuemat E as lubricant;
(3) heating certain hour, when melt begins to ooze downwards by shower nozzle, open the high-voltage D.C. generator power supply, add certain voltage, melt is being ejected on the receiving system of certain acceptance distance under the effect of high-pressure electrostatic, obtains the mLLDPE sub-micron fibers.
2. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 1, it is characterized in that: described in step (1), temperature is 150 ℃.
3. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 1, it is characterized in that: described in step (1), voltage is 0-30kV.
4. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 3, it is characterized in that: described in step (1), voltage is 29kV.
5. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 1, it is characterized in that: described in step (1), receiving range is 3cm.
6. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 1, it is characterized in that: described in step (2), the ratio of the quality of the quality of Tissuemat E and mLLDPE is 1:3.
7. the preparation method of Metallocenyl low density polyethylene (LDPE) sub-micron fibers according to claim 1, it is characterized in that: be 10min heat time heating time described in step (3), and voltage is 29 kV, it is certain that to accept distance be 3cm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037377A (en) * | 2014-05-22 | 2014-09-10 | 北京石油化工学院 | Preparation method for lithium battery membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08503525A (en) * | 1992-11-24 | 1996-04-16 | エクソン・ケミカル・パテンツ・インク | Polyolefin polymer fiber |
| US20050164586A1 (en) * | 2004-01-26 | 2005-07-28 | Autran Jean-Philippe M. | Fibers and nonwovens comprising polyethylene blends and mixtures |
| CN101663425A (en) * | 2007-03-22 | 2010-03-03 | 博里利斯技术公司 | Fibres, tapes or filaments comprising a polyethylene composition |
| CN101812734A (en) * | 2009-02-25 | 2010-08-25 | 北京化工大学 | Device for producing composite fibers through melt-electrospinning |
-
2013
- 2013-03-04 CN CN201310067619XA patent/CN103088445A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08503525A (en) * | 1992-11-24 | 1996-04-16 | エクソン・ケミカル・パテンツ・インク | Polyolefin polymer fiber |
| US20050164586A1 (en) * | 2004-01-26 | 2005-07-28 | Autran Jean-Philippe M. | Fibers and nonwovens comprising polyethylene blends and mixtures |
| CN101663425A (en) * | 2007-03-22 | 2010-03-03 | 博里利斯技术公司 | Fibres, tapes or filaments comprising a polyethylene composition |
| CN101812734A (en) * | 2009-02-25 | 2010-08-25 | 北京化工大学 | Device for producing composite fibers through melt-electrospinning |
Non-Patent Citations (1)
| Title |
|---|
| 赵娜等: "熔体静电纺丝法制备mLLDPE纤维的研究", 《新技术新工艺》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037377A (en) * | 2014-05-22 | 2014-09-10 | 北京石油化工学院 | Preparation method for lithium battery membrane |
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Application publication date: 20130508 |